TY - JOUR
T1 - An anionic, tetragonal copper(II) superoxide complex
AU - Donoghue, Patrick J.
AU - Gupta, Aalo K.
AU - Boyce, David W.
AU - Cramer, Christopher J.
AU - Tolman, William B.
PY - 2010/11/17
Y1 - 2010/11/17
N2 - Insight into copper-oxygen species proposed as intermediates in oxidation catalysis is provided by the identification of a Cu(II)-superoxide complex supported by a sterically hindered, pyridinedicarboxamide ligand. A tetragonal, end-on superoxide structure is proposed based on DFT calculations and UV-vis, NMR, EPR, and resonance Raman spectroscopy. The complex yields a trans-1,2-peroxodicopper(II) species upon reaction with [(tmpa)Cu(CH 3CN)]OTf and, unlike other known Cu(II)-superoxide complexes, acts as a base rather than an electrophilic (H-atom abstracting) reagent in reactions with phenols.
AB - Insight into copper-oxygen species proposed as intermediates in oxidation catalysis is provided by the identification of a Cu(II)-superoxide complex supported by a sterically hindered, pyridinedicarboxamide ligand. A tetragonal, end-on superoxide structure is proposed based on DFT calculations and UV-vis, NMR, EPR, and resonance Raman spectroscopy. The complex yields a trans-1,2-peroxodicopper(II) species upon reaction with [(tmpa)Cu(CH 3CN)]OTf and, unlike other known Cu(II)-superoxide complexes, acts as a base rather than an electrophilic (H-atom abstracting) reagent in reactions with phenols.
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U2 - 10.1021/ja106244k
DO - 10.1021/ja106244k
M3 - Article
C2 - 20977226
AN - SCOPUS:78449253792
SN - 0002-7863
VL - 132
SP - 15869
EP - 15871
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 45
ER -